Search

Rod-like particles have attracted increasing attention because of their unique shape-dependent properties, which enable their superior performance compared to their isotropic counterparts. Thus, rod-like particles have potential applications in many fields, especially in biomedicine. However, the fabrication of uniform rod-like particles is challenging because of the principle of interfacial energy minimization. Herein, we present a facile, rapid, and cost-effective strategy for preparing starch-based microrods with tunable aspect ratios via shear-assisted antisolvent-induced nanoprecipitation and solidification. The preformed spherical particles swollen by the mixed solvent were elongated by the shear force and solidified in rod-like shape by antisolvent induction. The resulting starch-based microrods can encapsulate hydrophobic active substances and be modified with functional groups, indicating their potential applications as drug carriers and biologically active materials. The formation mechanism of the starch-based microrods discovered in this study provides a new perspective on the fabrication of rod-like polymer particles.

As emerging eutectic mixtures, deep eutectic electrolytes (DEEs) show unique properties for Li-metal batteries (LMBs). However, the limited choice and inferior electrode compatibility hinder their further development in LMBs. Herein, we report a new 1,2-dimethylimidazole (DMIm)-based deep eutectic gel polymer electrolyte induced by Li-N interaction. We demonstrate that incorporating electron-withdrawing polyvinylidene difluoride (PVDF) polymer into the DMIm-based DEE changes the coordination environment of Li

There is a pressing need around the world to develop novel functional biodegradable materials to separate oil/water mixtures and emulsions completely. Recently, superhydrophilicity and underwater superoleophobicity materials have been attracted attention due to their high efficiency in oil/water separation. However, it is still a challenge to prepare materials that combine oil/water separation and water purification in an environment-friendly way. In this work, biodegradable starch-based nanospheres (SNPs) coated filter paper was prepared in a low-cost, simple, and environmentally friendly manner. The SNPs coating could not only help to change the wettability of the substrate material but also build the hierarchical micro and nano structures which are conducive to separation and purification process. After modification by coating SNPs, the filter paper exhibited excellent performance in a wide range of oil/water mixtures or emulsions separation and the wettability of the filter paper could be regulated by adjusting the pH value. The modified filter paper presented good recyclability after several separation process. Furthermore, the as-prepared filter paper could also remove water-soluble contaminants during the oil/water separation process, thus realizing to combine separation and purification process in one single step. This biodegradable starch-based separating material with good separation performance, stability and recyclability has significant application potential in practical separation and purification process.

Pickering high internal phase emulsions (HIPEs) stabilized solely by bioderived starch-based particles hold potential for application in the food and pharmaceutical fields. This paper reports the use of a thermoresponsive 2-hydroxy-3-butoxypropyl starch (HBPS) particle as a representative natural biocompatible material for use as an effective stabilizer for HIPE formation. HBPS is synthesized by using butyl glycidyl ether as a hydrophobic reagent to change the hydrophobic–hydrophilic balance of starch, and then starch-based particles are fabricated by a simple nanoprecipitation procedure. The size of particles increased with an increase in temperature, and the particles are essentially monodisperse with a PDI of about 0.1 when the temperature was above 15 °C. These HBPS particles were subsequently used as an effective stabilizer to fabricate stable oil-in-water (o/w) Pickering HIPEs with an internal phase volume of 80% at different stabilizer concentrations. The results demonstrated that increasing the particle concentration is conducive to the formation of stable Pickering HIPEs with greater stiffnesses. In addition, the nutraceutical material (β-carotene) was encapsulated into HIPEs and in vitro release experiments revealed that the release in this system can be controlled by adjusting the temperature.

To realize intelligent and low-cost protective materials, the development of compounds with smart stress-responsive properties and self-healing abilities over a wide temperature range is a major research goal. In this study, a series of impact hardening polymers (IHPs) with stress-responsive properties and self-healing ability in low temperature were synthesized via the condensation copolymerization of silicone polymers with various chain lengths and boron contents. The results of rheological analysis indicate that the IHPs have self-healing ability at low temperatures (healing times of less than 30 h and healing efficiencies better than 80% at −25 °C). Moreover, the relative shear stiffening effect (RSTe), which describes the stress-responsive ability of the IHP, exceeded 2000. In addition, the self-healing mechanism of IHP was investigated by Fourier transform infrared spectroscopy microscopy and pulsed 1H-NMR measurements. The results suggested that reversible dynamic cross-linking arising from the boron compound and the reduction in the threshold entanglement density owing to the longer length of the flexible polymeric backbone is crucial to impart low-temperature self-healing ability and stress-responsive properties to IHP.

Inverse Pickering emulsions stabilized by naturally derived particles are of interesting during the past decade. In this study, starch-based nanoparticles were used as a particulate emulsifier to stabilize a w/o Pickering emulsion. The effects of particle concentration and oil volume fraction on the emulsion type and stability were investigated in detail. Catastrophic phase inversion from o/w to w/o emulsions occurred at a volume fraction of oil of 0.3-0.4, without altering the particle wettability. Further, a linear relation existed between the average droplet diameter and total amounts of starch-based nanoparticles. The obtained starch-based nanoparticles also served as a Pickering stabilizer to conduct a w/o Pickering polymerization. Raspberry-like thermoresponsive starch-poly(N-isopropyl acrylamide) nanocomposites with a well-defined structure were synthesized.

As one of the most prevalent porous media, rock contains a large number of pore throats of varying size and shape. It is essential to analyze the complex pore network structure and to define the network structural features to reveal the microscopic mechanism of the rock permeability. In this paper, based on the complex network theory and CT scanning technology, sandstone is used as an example to study the structural characteristics of the rock network with different porosities. The results show that the structural characteristics of the sandstone seepage network are consistent with BA scale-free network, whose average path length increases with the size of the network. At the same time, the porosity of the sandstone is strongly influenced by the number of throat in the rock pore network. Furthermore, our analysis concludes that a few pores with a large number of connections contribute significantly to the overall connectivity of the sandstone seepage network. Removing the ‘hub’ pores increased the average path length of the entire network by 27.63-37.26%, which could not be achieved by randomly removing method. While the sandstone seepage network has better fault tolerance and robustness to external random attacks, this study provides a new approach to study the mechanisms of fluid storage and migration in porous media.

Adsorptive membranes offer an effective mode to remove heavy metal ions from contaminated water, due to the synergies made possible by low-cost, high-affinity adsorbents and highly scalable filtration in one system. However, the development of adsorptive membranes is hampered by their instability in the aqueous phase and low binding affinity with a broad spectrum of heavy metals in a reasonable flux. Herein, a regenerated cellulose support membrane is strongly grafted with stable and covalent-bonded polyelectrolyte active layers synthesized by a reactive layer-by-layer (LBL) assembly method. The LBL assembled layers have been successfully tested by scanning electron microscopy, Fourier-transform infrared spectroscopy and X-ray photo-electron spectroscopy. The covalent bonding provides the membrane with long-term stability and a tunable water flux compared to a membrane assembled by electrostatic bonding. The maximum adsorption capacity of the membrane active layers can reach up to 194 mg/g, showing more efficient adsorption at lower heavy metal concentration and higher pH value of feed solution. The membrane can remove multiple ions, such as Cu, Pb, and Cd, by adsorption and is easy to be regenerated and recovered. The strong covalent bonding can extend the membrane lifetime in water purification to remove multiple heavy metals at high efficiency.

Nonspherical colloidal particles with various geometries and different compositions have attracted tremendous attention and been widely researched. The preparation of polymer colloidal particles with controlled shapes by seeded polymerization is recognized as the most promising technique owing to the precise control of various morphologies and using non-cross-linked seed particles are of particular interest. Seeds particles derived from natural biopolymers are seldom applied. Hence, non-cross-linked starch-based seed could be used to fabricate the anisotropic particles by soap-free seed polymerization. Non-cross-linked starch-based seed particles were prepared by a nanoprecipitation method. Starch/polystyrene composite colloidal particles with shape-tunable were fabricated by soap-free seeded polymerization using starch-based seed. The effect of the polymerization time, monomer feed ratio and seed type were investigated. The seed particles with a single- or multi-hole structure were obtained after swelling with styrene. The resulting particles including golf-like, raspberry-like, octahedron-like and snowman-like structures, was fabricated on the polymerization process. This study firstly reports that the morphology of composite particles from golf-like to snowman-like at high monomer feed ratio using starch-based seed. At low monomer feed ratio, raspberry-like particles were obtained by surface nucleation increasing process. In addition, seed type also effect the morphology of composite particles.

A series of chemically cross-linked microgel composite hydrogels (MCH gels) with excellent toughness and stretchability were prepared using core–shell polymer microspheres as cross-linking junctions. In our strategy, MCH gels are obtained by connecting microspheres with polyacrylamide (PAAm) chains chemically grafted onto their surfaces, where an organic cross-linking agent is completely unnecessary. The mechanical behavior of the MCH gels was analyzed, and superresolution fluorescence microscopy and scanning electron microscopy were used to investigate their toughening mechanism. The results indicated that the homogeneous network structure resulting from the good compatibility between the core–shell microspheres and matrix was an important reason for the excellent toughness of the MCH gels. In addition to interactions among H bonds in the grafted PAAm chains, reversible deformation of the core–shell microspheres acting as cross-linking junctions, which arises from the flexibility of the microspheres, and the effect of cavitation between the microspheres and matrix could also effectively dissipate energy during deformation of the MCH gels.

We developed tough, rapid-recovery composite hydrogels that are fabricated via core–shell microgel covalent bonding and Fe3+ dynamic metal coordination cross-linking. First, core–shell microgels are used as cross-linking agents and initiators to prepare homogeneous hydrogel networks with rapid recovery in the absence of an organic cross-linking agent. The toughness and recoverability of the composite hydrogels can be improved by adding the dynamic reversibility of ionic cross-linking. Owing to the synergistic effect of microgel covalent bonding, Fe3+ coordination cross-linking, and H-bond cross-linking, the multi-cross-linked composite hydrogels exhibit excellent toughness and a fast recovery rate. These characteristics demonstrate that the dynamic reversibility of the ionic cross-linking can significantly improve the toughness and recoverability of the hydrogels. In addition, the core–shell microgels play a key role in toughening the hydrogels and accelerating their recovery by transferring stress to grafted polymer chains and homogenizing the hydrogel network.

The convenient synthesis of core-shell nanoparticles containing degradable components is very desirable given the potential applications of such nanoparticles in biomaterials. A facile approach for producing monodisperse starch-polystyrene nanocomposites with well-defined core-shell structures in the absence of a surfactant was developed. The initially-formed Pickering emulsions underwent conversion into seeded emulsions during the polymerization, wherein the amphiphilic starch-based nanospheres (SNPs) serve as stabilizer and seed. A possible mechanism for this transition was explored based on the morphology and size variations of the emulsion droplets and the resultant nanospheres. The effects of the monomer concentration, SNP content and size, and pH on the core-shell nanospheres were investigated. With increasing monomer concentration, the core size of the particles remained almost unchanged, while the shell layer thickness increased almost linearly. The size of the core-shell nanospheres can be regulated by adjusting the pH and the SNP content and size.

We study biosourced core-shell particles with a starch-based core and thermo-responsive polymer brush shell using surface-initiated single-electron transfer living radical polymerization (SI-SET-LRP) as a Pickering stabilizer. The shell endows the Pickering stabilizer with reversible emulsification/demulsification of oil and water properties. The initiator attached to the starch-based nanosphere (Br-SNP) core particle was first fabricated using the precipitation method. Subsequently, dense poly( N-isopropylacrylamide) (PNIPAM) brush graft-modified starch-based nanoparticles (SNP- g-PNIPAM) were obtained via the SI-SET-LRP process. Interfacial properties of the resultant particles were analyzed by interfacial tensiometer measurements, as were the effects of the grafted polymer chain length and temperature on the interfacial activity. Pickering emulsion was obtained using SNP- g-PNIPAM particles as the stabilizer. The effect of the concentration of the Pickering stabilizer on the size of emulsion droplets was analyzed. The emulsification/demulsification process of the Pickering emulsion can be reversed and easily repeated by changing the temperature.

Conventional approaches to generating double emulsions are cumbersome, complicated, and based on a two-step emulsification process using a combination of two distinctive surfactants. In this work, the surface properties of diatomite particles were successfully tailored by chemical modification with palmitoyl chloride. The properties of the resulting diatomite particles changed from the original hydrophilicity to hydrophobicity, leading to straightforward stabilization of oil-in-water-in-oil (O/W/O) Pickering double emulsions by a one-step emulsification process. Pickering double high internal phase emulsions (HIPEs) with an internal phase up to 80 vol% could be produced solely using the modified diatomite particles. The water-in-oil (W/O) droplet sizes of these HIPEs were much larger than the droplets of conventional nanoparticle-stabilized Pickering HIPEs. Furthermore, using the O/W/O Pickering double emulsions as templates, the porous polymer particles were fabricated. In addition, it was demonstrated that the wide particle size distribution of diatomite particles and modified heterogeneity were the reasons for the formation of multiple emulsions.

There are a large number of pores and throats inside the rock, with different magnitude and shape, whose connection is complex[1–3]. Based on the complex network theory, combined with X–ray CT scan and image processing technology, we used sandstone as an example to study the structural characteristics of rock network of different porosities. The experimental results show that the seepage network of sandstone is similar to the BA scale-free network in the structural characteristics. The average path length of sandstone generally increases with the increase of network magnitude. The average of number of edges of node plays a dominant role for the porosity of sandstone. It is inferred that in the large number of pores, few pores with a number of connections have an important role in the overall connectivity of the sandstone seepage network. At the same time, sandstone seepage network has better fault tolerance rate and robustness to external random attacks. The results of this paper may provide a new idea for the study of fluid storage and migration mechanisms in porous materials and the application of complex network theory in interdisciplinary fields.

Understanding the interfacial activity of polysaccharide nanoparticles adsorbed at oil–water interfaces is essential and important for the application of these nanoparticles as Pickering stabilizers. The interfacial properties of starch-based nanospheres (SNPs) at the interface of an n-hexane–water system were investigated by monitoring the interfacial tension at different bulk concentrations. The three-phase contact angle (θ) and the adsorption energy (ΔE) increased with increasing size and degree of substitution with octenyl succinic groups (OSA) in the particles. Compared with the OSA-modified starch (OSA-S) macromolecule, the SNPs effectively reduced the interfacial tension of the n-hexane–water system at a relatively higher concentration. These results and the method reported herein are useful for selecting and preparing polysaccharide nanoparticles as Pickering stabilizers for oil–water emulsions.

We developed tough, rapid-recovery composite hydrogels that are fabricated via core-shell microgel covalent bonding and Fe

Biodegradable polymer nanocomposites with bioresource starch-based nanoparticles (SNPs) as reinforcing fillers for polycaprolactone (PCL) were prepared by melt blending. Scanning electron microscopy observation revealed that SNPs as spherical particles were evenly dispersed in the PCL matrix without any aggregation even with the content of SNPs increasing to 10wt% in the nanocomposite. Consequently, the rheological performances of PCL have been improved efficaciously after incorporation with SNPs as well as mechanical properties, especially with a percolation network structure of SNPs in the PCL matrix formed. In addition, the enzymatic hydrolysis experiments showed a more interesting behavior that the hydrolysis rates had been accelerated apparently in the nanocomposites than that in the neat PCL as observed. Such high performance nanocomposites may have great potential in expanding the utilization of starch from sustainable resources and the practical application of PCL-based biodegradable materials.